Two cases of lanthanide (Ln)-implanted arsenotungstates, K17Na2H5[{(As2W19O67(H2O))Ln(H2O)2}2(C2O4)]·87H2O (Ln = Eu (1), Ln = Tb (2)) and their codoped derivatives EuxTb1-x-POM (x = 0.01 (3), x = 0.04 (4), x = 0.1 (5), x = 0.2 (6)) were prepared and further characterized by powder X-ray diffraction, infrared spectra, and thermogravimetric analyses. An X-ray structural analysis of 1 and 2 indicates that they both present a dimeric oxalate-bridged Ln3+-implanted lanthanide arsenotungstate polyanion structure. Under the O → W LMCT excitation at 265 nm of arsenotungstate polyanions, the emissions of Ln3+ ions in 1 and 2 are sensitized and the lifetimes are prolonged. Codoped compounds 3-6 demonstrate a color-tunable emission from green to red by adjusting the Eu3+/Tb3+ ratio. Emission spectra and time-resolved emission spectroscopic studies were performed for 3 to further authenticate the energy transfer processes from excited arsenotungstates to the Eu3+ and Tb3+ metal ions and also between the Eu3+ and Tb3+ centers. More interestingly, 1 is an effective fluorescent probe for the recognition and detection of Ba2+ ions in aqueous solution. The optical properties of the Ln-implanted arsenotungstate compounds not only expressly reveal distinctive energy transfer processes in those compounds but also broaden the application of POM-based materials in the fluorescence sensing field.